JP2002154997A - Method for producing cyclopentanol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method by which cyclopentanol is produced from cyclopentene with high yield and high selectivity while suppressing generation of by-products. SOLUTION: This method for producing the cyclopentanol is characterized by using a protonic zeolite having >=10 ratio of (SiO2)/(Al2O3) and regulated in x-ray diffraction pattern substantially to the pattern represented by the table 1 as a catalyst in the method for producing the cyclopentanol by hydrating the cyclopentene in the presence of the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a catalytic hydration reaction for producing cyclopentanol by reacting cyclopentene with water in the presence of a zeolite catalyst.

[0002]

2. Description of the Related Art Conventionally, mordenite, clinobutyrolite or faujasite zeolite (JP-B-47-45323) has been used as a zeolite catalyst used in a hydration reaction.
Publication), ZSM zeolite (JP-B 2-3105)
No. 6 is known.

However, methods using these catalysts are not industrially satisfactory due to low catalytic activity and low selectivity of cyclopentanol. In particular, when a ZSM-5 zeolite proposed as a catalyst for producing cyclohexanol is used, the selectivity of cyclopentanol is extremely low, and as a result, the yield of cyclopentanol is low. . For example, JP-A-60-10
Japanese Patent No. 4028 describes that as a result of a hydration reaction of cyclopentene using ZSM-5, the concentration of cyclopentanol produced was 1.4% by weight, and there was no other product. . In addition, Japanese Patent Application Laid-Open No. 5-97736
In the publication, cyclopentanol is obtained by a catalytic hydration reaction of cyclopentene at a concentration of 12.5% by weight and a selectivity of 99.
Although it was described that it was obtained at 5%, when the hydration reaction of cyclopentene was actually carried out using a ZSM-5 zeolite catalyst, the concentration of produced cyclopentanol was 2%.
% By weight and the selectivity was 30% or less.

In the above reaction, the cyclopentanol concentration and the selectivity are low because the cyclopentene is hydrated to produce cyclopentanol, and then the reaction proceeds further to produce dicyclopentyl ether. .
This is because cyclopentanol produced by the hydration reaction of cyclopentene has a higher solubility in water than cyclohexanol, so the transfer rate to the organic phase is slow, and the catalyst ZSM-5 is linked in three dimensions. With pores
It is considered that this is advantageous for the diffusion of cyclopentene and the generated cyclopentanol, so that the sequential reaction proceeds.

[0005] On the other hand, there have been disclosed many methods for adding an organic solvent using a zeolite catalyst for the purpose of improving the yield of a cyclic alcohol by a hydration reaction of a cyclic olefin. For example, JP-A-58-194828 discloses alcohols having 1 to 10 carbon atoms, halogenated hydrocarbons, ethers, organic solvents such as acetone and methyl ethyl ketone, JP-A-62-120333 and JP-A-62-120333. JP-A-126141 discloses phenols, JP-A-64-13044 discloses fluoroalcohols,
JP-A-1-254634, JP-A-1-31344
No. 7, JP-A-4-247041 and JP-A-5-255162 report a method of adding an aliphatic carboxylic acid and a benzoic acid, respectively, to a hydration reaction system.

However, in the method of adding the above-mentioned solvent to the hydration reaction system, the yield of cyclopentanol is improved but the selectivity is insufficient, or the selectivity is improved but the yield is insufficient. There were problems such as the presence of such a compound, and it was not effective in improving both the yield and the selectivity.

As a method of improving the selectivity, Z
Although a method using a zeolite having a smaller pore size than SM-5 is also conceivable, there is a problem that the catalytic activity is extremely low and the target product cannot be obtained efficiently.

Further, a method of using a zeolite having a small pore size by exchanging a part of the proton type zeolite with a metal ion is well known (for example,
J. Catalysis. , 9 , 225 (196
7). J. Catalysis. , 10 , 34 (19
68). And J. Catalysis. , 33 , 48
6 (1974) and the like). However, in the case of performing ion exchange in advance, the sodium salt of zeolite must be treated with a chloride, nitrate or ammonium salt of the metal to be exchanged, and then calcined, which complicates the production process of the catalyst. This is a problem in implementing the method.

As a technique related to the present invention, Patent No. 2
No. 754,063 discloses "X-ray diffraction patterns containing values substantially as shown in Table 1 of the specification, adsorption of water vapor of more than 10 wt%, and adsorption of cyclohexane vapor of more than 4.5 wt%. Of synthetic porous crystalline material characterized by having a capacity and an adsorption capacity for n-hexane vapor of more than 10 wt%. However, although the publication discloses that the corresponding alcohol can be obtained by a hydration reaction of an olefin having 2 to 7 carbon atoms, the content of the hydration reaction includes production of a synthetic porous crystalline substance and hydration of propylene. This is a reaction and there is no description that cyclopentanol can be produced from cyclopentene as in the present invention.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and a method for producing cyclopentanol from cyclopentene with high yield and high selectivity while suppressing the generation of by-products. The task is to provide

[0011]

Means for Solving the Problems The present inventors have solved the above problems.
To solve this problem, cyclopente was used with zeolite as a catalyst.
About the method of producing cyclopentanol by hydrating
I studied hard. As a result, as a catalyst, SiO 2_Two/ Al
_TwoO_ThreeThe ratio is 10 or more and the X-ray diffraction pattern is substantially
Is defined by the pattern in Table 1 and the Langmuir table
Area is 300m ^Two/ g or more proton type zeolite
By using it, cyclopentanol can be obtained in high yield and
The present invention was found to be able to be manufactured with high selectivity, and the present invention
Was completed.

That is, the present invention relates to a method for producing cyclopentanol by hydrating cyclopentene in the presence of a catalyst, wherein the ratio of SiO ₂ / Al ₂ O ₃ is 10 or more and the X-ray diffraction pattern is substantially Specifically, the present invention provides a method for producing cyclopentanol, which comprises using a proton type zeolite defined by the pattern shown in Table 1 as a catalyst.

In the present invention, the catalyst may be La
It is preferable to use a catalyst having an ngmuir surface area of 300 m ² / g or more.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, the SiO ₂ / Al ₂ O ₃ ratio is 10 or more, and the X-ray diffraction pattern is substantially defined by the pattern shown in Table 1. As a limiting condition, the Langmuir surface area is 300 m
It is characterized by using a proton type zeolite having a mass of ² / g or more.

In the present invention, as the zeolite catalyst,
When a zeolite having a SiO ₂ / Al ₂ O ₃ ratio of less than 10 is used, the selectivity from cyclopentene to cyclopentanol decreases. The Langmuir surface area can be determined, for example, by a known method such as a BET method determined from the amount of nitrogen adsorbed on the zeolite surface at the temperature of liquid nitrogen. If the Langmuir surface area of the zeolite catalyst used is less than 300 m ² / g, the catalytic activity will be poor.

Zeolite has the property that cations that electrically neutralize (AlO ₄ ) ⁻ in the crystal can be easily exchanged for other cations. In the present invention, the proton type zeolite is formally referred to as a basic form of N
Zeolite in which a ⁺ is exchanged for a proton. Proton-type zeolites can be prepared by, for example, a method of treating Na ⁺ -type zeolite with dilute hydrochloric acid, a method of first exchanging Na ⁺ -type zeolite with ammonium ions, and then heating to drive off ammonia.

The zeolite used in the present invention is
It has an X-ray diffraction pattern defined in Table 1 below. This X-ray diffraction pattern is characteristic of the zeolite catalyst used in the present invention.

[0018]

[Table 1]

These values can be determined by a standard method using copper K-alpha rays as an X-ray source and using an X-ray diffractometer having a diffractometer equipped with a scintillation counter and a computer linked thereto. That is, the peak height I and 2θ (θ is the Bragg angle) are determined using an algorithm on a computer linked to the diffractometer, and from these values, the relative intensity: 100 ×
I / I ₀ (I ₀ is the height of the strongest line or peak.)
And the lattice spacing d expressed in angstrom units (Å) can be obtained.

In Table 1, the relative intensity is represented by the symbol W
= Weak, M = medium, S = strong and VS = very strong. W = 0-20 M = 20-40 S = 40-60 VS = 60-100

The zeolite used in the present invention may be in any form, for example, powder, granules and the like. Alumina, silica, titania, clay compounds and the like can also be used as a carrier or a binder.

The form of the hydration reaction may be any commonly used form such as a batch type, a semi-batch type, a fluidized bed type, and a fixed bed continuous flow type, and is not particularly limited. The conditions of the hydration reaction are not particularly limited as long as the catalyst is present in any one of a liquid phase of an aqueous phase, an organic phase, or a mixed phase of both.

The amount of the zeolite catalyst used is usually in the range of 0.001 to 200, preferably 0.05 to 20, by weight of catalyst / cyclopentene. The amount of water used is not particularly limited, but is 0.10 to 100 parts by weight, preferably 0.5 to 100 parts by weight, per part by weight of the raw material cyclopentene.
It is in the range of 50 parts by weight.

The reaction temperature is preferably a low temperature in order to suppress the side reaction while shifting the equilibrium of the hydration reaction of cyclopentene toward the cyclopentanol side, but a higher reaction temperature is more advantageous in terms of the reaction rate. is there. Therefore, in the present invention, the reaction temperature is usually 50 to 200 ° C, preferably 80 to 200 ° C.
It is in the range of 150 ° C.

The pressure in the reaction system is preferably equal to or higher than the pressure required to keep cyclopentene, water and the organic solvent in a liquid phase under the reaction conditions. However, a lower pressure may be used as long as cyclopentene is sufficiently dissolved in the reaction solution. Further, the pressure in the reaction system can be adjusted by an inert gas such as nitrogen gas. The reaction time or residence time is usually 0.1
10 to 10 hours, preferably 0.5 to 5 hours.

In the hydration reaction, an organic solvent can be used. The organic solvent is not particularly limited as long as it dissolves cyclopentene and cyclopentanol and is inert to the hydration reaction, but is not limited to alcohol solvents, ketone solvents, phenol solvents, ether solvents, and hydrocarbon solvents. And a mixed solvent composed of two or more of these.

Examples of the alcohol solvent include cyclohexanol, 1-methylcyclohexanol,
Cyclic alcohols such as methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol; cyclic alcohols such as cycloheptanol and cyclooctanol; glycol ethers such as ethylene glycol monomethyl ether and polyethylene glycol monolaurate. No. Examples of the ketone solvent include 4-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2,4-dimethyl-3-pentanone, acetophenone, 2,4-pentanedione,
Examples include 3-butanedione, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, and the like.

Examples of phenol solvents include phenol, cresol, xylenol, ethylphenol, trimethylphenol, isopropylphenol,
Examples include phenols and substituted phenols such as t-butylphenol, phenylphenol, chlorophenol, hydroquinone monomethyl ether and 4-hydroxybenzoic acid; and naphthols such as 1-naphthol and 2-naphthol. Examples of ether solvents include dioxane, diisopropyl ether, dibutyl ether,
Examples include diamyl ether, dicyclopentyl ether, and ethylene glycol dimethyl ether. Examples of the hydrocarbon-based solvent include chain aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, and decalin; benzene, toluene, xylene, Examples include aromatic hydrocarbons such as ethylbenzene, mesitylene, and tetralin.

The amount of the organic solvent to be used is generally 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 1 part by weight of the starting material cyclopentene.

The reaction system is preferably maintained in an atmosphere of an inert gas such as nitrogen, hydrogen, helium, argon and carbon dioxide. The content of oxygen in the inert gas is preferably smaller, and the oxygen content is usually 100 ppm or less, preferably 20 ppm or less.

[0031]

EXAMPLES Next, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples, and the type of catalyst used, reaction conditions, and the like are not departed from the gist of the present invention. Can be changed freely.

(1) Preparation of catalyst 6.8 g of NaAlO ₂ (manufactured by Wako Pure Chemical Industries, Ltd.), NaOH
8.6 g (manufactured by Wako Pure Chemical Industries, Ltd.) and ion-exchanged water 460
g in a bucket and stirred to obtain a clear solution A.
Next, 350 g of ion-exchanged water and 41 g of hexamethyleneimine were put into another polybucket to form a mixed solution, and 60 g of silica (Cab-O-Sil.M7D) was added thereto, followed by stirring for 30 minutes to obtain gel B. Further, the gel B is added little by little to the solution A with stirring, and the mixture is further stirred for 2 hours after the addition of the gel B is completed, whereby SiO ₂ : A
Mixed gel C having a ratio of l ₂ O ₃ : hexamethyleneimine: Na ₂ O: H ₂ O of 1: 0.033: 0.5: 0.15: 45
I got

The obtained mixed gel C was transferred into an autoclave having an inner wall coated with Teflon (registered trademark),
15 hours over 2 hours while stirring at a rotation speed of 60 rpm.
After the temperature was raised to 0 ° C, stirring was continued at 150 ° C for 7 days. The crystals precipitated from the reaction mixture were separated by filtration, washed, dried at 125 ° C. overnight, and then dried at 550 ° C. in an air atmosphere.
For 10 hours. Further, the obtained fired product is 0.2M
The catalyst A was obtained by ion exchange with an aqueous ammonium nitrate solution and calcining at 500 ° C. for 5 hours in an air atmosphere. The resulting catalyst A has a Langmuir surface area of 548.
m ² / g and measured by ICP emission spectroscopy.
The O ₂ / Al ₂ O ₃ ratio was 30. Further, the X-ray diffraction (XRD) measurement results (CuKα) of Catalyst A were as shown in Table 2, and were consistent with the XRD pattern specified in Table 1.

[0034]

[Table 2]

(Example 1) Hydration reaction of cyclopentene 4 g of cyclopentene, 5.4 g of water, 5 g of catalyst A and a stirrer chip were placed in a 50 ml autoclave equipped with a thermocouple, and reacted at 120 ° C for 18 hours under a nitrogen atmosphere. Was. After completion of the reaction, methanol was added to the reaction solution to homogenize it, and the catalyst was taken out by filtration. After washing the catalyst with methanol, the washings and the supernatant of the centrifugation were combined and analyzed by gas chromatography using cyclohexanol as an internal standard substance. At this time, the conversion of cyclopentene was 4.8 mol%, the selectivity of cyclopentanol was 99.0 mol%, and the selectivity of dicyclopentyl ether as a by-product was 0.8 mol%.

Comparative Example 1 In Example 1, ZSM-5 (SiO ₂ / Al ₂ O ₃ ratio =
The reaction was carried out in the same manner as in Example 1 except that 25) was used. At this time, the conversion of cyclopentene was 4.2 mo.
1%, selectivity of cyclopentanol is 93.3 mol
%, And the selectivity for dicyclopentyl ether as a by-product was 6.4 mol%.

[0037]

As described above, according to the production method of the present invention, the yield of cyclopentanol, which is the target product, is improved while suppressing the formation of by-products during the hydration reaction of cyclopentene. be able to.

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Claims (2)

[Claims] We claim: 1. hydrating cyclopentene in the presence of a catalyst in a process for producing cyclopentanol, SiO ₂ /
A method for producing cyclopentanol, wherein an Al ₂ O ₃ ratio is 10 or more and a proton-type zeolite whose X-ray diffraction pattern is substantially defined by the pattern shown in Table 1 is used as a catalyst. 2. The method for producing cyclopentanol according to claim 1, wherein a zeolite catalyst having a Langmuir surface area of 300 m ² / g or more is used as the catalyst.